Cyclic cyanodithioimidocarbonate and its preparation

ABSTRACT

COMPOUNDS OF THE FORMULA   R-N=C&lt;(-S-(CH2)N-S-)   AND METHODS OF MAKING AND USING THEM.

3,755,363 CYCLIC CYANODITHIOIMIDOCARBONATE AND ITS PREPARATION RichardV. Timmons, Marysville and Lawrence S. Wittenbrook, Columbus, Ohio,assignors to The 0. M. Scott & Sons Company, Marysville, Ohio NoDrawing. Filed Sept. 12, 1966, Ser. No. 578,514 Int. Cl. C07c 69/00 US.Cl. 260-327 M 2 Claims ABSTRACT OF THE DISCLOSURE Compounds of theformula C n C=NR \2)/ and methods of making and using them.

This invention relates to novel chemical compounds, and morespecifically, to novel compounds having valuable growth regulatingproperties and to their preparation and use.

The compounds to which the present invention relates can be representedby the following general formulae.

wherein n is 1, 2, or 3, and R is i JNH or -OEN S III wherein R is CH(CH with m being 0-5, or aryl.

The compounds of the present invention may also be represented by thegeneral formula 0 .;o=N-R s n being 1, 2, or 3; R being 5 ll lg ON, -CNHor NH,

when n is 1 or 3 and UnitcdStates Patent 0 m 3,755,363 Patented Aug. 28,1973 ice and R being hydrogen, CH (CH with m being 0-5, or aryl; R beingCH (CH with m being 0-5 or aryl and R being hydrogen, CH (CH with mbeing 0-5, or aryl; R being CH (CH when R is CH (CH with m being 0-5,aryl when R; is aryl, and aryl or hydrogen when R is hydrogen.

Typical radicals R include hydrogen and methyl; R include n-hexyl,phenyl and chlorophenyl; R include hydrogen, methyl and phenyl; Rinclude methyl, phenyl, nitrophenyl, chlorophenyl, dichlorophenyl andhydrogen.

The following are typical compounds of the present invention. Thelisting includes only representative, not all, compounds of the presentinvention.

Cyclic methylene cyanodithioimidocarbonate Cyclic ethylenecyanodithioimidocarbonate Cyclic propylene cyanodithioimidocarbonate(2-( 1,3-dithiolaneidene) urea 2-( 1,3-dithiolaneidene) thiourea1-phenyl-3-(2-(1,3-dithiolaneidene) urea 1,1-dimethyl-3-(2-(1,3-dithiolaneidene) urea 1-(2-chlorophenyl)-3-(2-(1,3-dithiolaneidene)urea 1-(3-chlorophenyl)-3-(2-(1,3-dithiolaneidene) urea1-(4-chlorophenyl)-3-(2-(1,3-dithiolaneidene) urea 1- 3,4-dichlorophenyl)-3-(2-(1,3-dithiolaneidene) urea1-(2-nitrophenyl)-3-(2-(1,3-dithio1aneidene) urea1,l-dipheny1-3-(2-(1,3-dithiolaneidene) urea1-phenyl-3-(2-(1,3-dithiolaneidene) thiourea n-Hexyl N- (2-(1,3-dithiolaneidene) carbamate Phenyl N-(2-(1,3-dithiolaneidene)carbamate 3-chlorophenyl N- (2-( 1,3-dithiolaneidene) carbamate4-chlorophenyl N- (2- 1,3-dithiolaneidene) carbamate 0ne of theimportant advantages of compounds disclosed herein, is that they arehighly active growth regulators for a variety of biological systems andare substantially less expensive to prepare than other compounds withthe same general properties.

From the foregoing it will be apparent that one important object of thepresent invention is to provide novel growth regulating compounds andcompositions.

A related and also important object of the present invention is toprovide growth regulating compounds and compositions which aresubstantially less expensive than those heretofore known with comparableproperties.

In conjunction with the foregoing, another important object of thisinvention resides in the provision of novel processes for preparing thecompounds of the invention.

A further important and related object of the present invention residesin the provision of novel methods of biological growth regulation whichemploy the compounds of the present invention.

Further objects and advantages and other novel fea tures of the presentinvention will become obvious to those skilled in the arts to which thisinvention pertains from the following detailed description of exemplaryembodiments of the invention and the appended claims.

Methods of preparing the compounds of this invention are set forth inthe following examples in which all parts are parts by weight and alltemperatures are expressed in degrees centigrade.

Type I compounds wherein n is 2 or 3 can be prepared by reactingdipotassium cyanodithioimidocarbonate with a dibromoalkane having 2 or 3carbon atoms as shown by the following equation:

"The reaction illustrated in the foregoing equation is described in moredetail in the following example, which relates to the preparation ofcyclic ethylene cyanodithioimidocarbonate.

EXAMPLE I Preparation of cyclic ethylene cyanodithioimidocarbonate Amixture of 19.4 parts of 1,2-dibromoethane in 4.1 parts of acetone wasadded dropwise, while stirring and under nitrogen,- to a mixture of 20parts of dipotassium cyanodithioimidocarbonate in 57.1 parts of acetoneand 87.6 parts of water. The reaction mixture was stirred 21 hours undernitrogen at room temperature as a precipitate slowly formed. The mixturewas then diluted with 299 parts of ice water and filtered, and the solidwas recrystallized to give previously unknown cyclic ethylenecyanodithioimidocarbonate.

The cyclic ethylene cyanodithioimidocarbonate (M.P. 7981) prepared bythis novel process was found to have the following elemental analysis:

Calculated for C H N S (percent): C, 33.31; H, 2.80; S, 44.47. Found(percent): C, 33.90; H, 2.79; S, 44.96.

Cyclic propylene cyanodithioimidocarbonate (M.P. 99- l02 prepared by thesame novel process was found to have the following elemental analysis:

Calculated for C H N S (percent): C, 37.95; H, 3.82; S, 40.53. Found(percent): C, 37.7 8; H, 3.51; S, 40.60.

Cyclic methylene cyanodithioimidocarbonate, a type I compound, can beprepared by reacting dipotassium cyanodithiomidocarbonate with methyleneiodide as shown in the following equation:

Preparation of cyclic methylene cyanodithioimidocarbonate is illustratedin greater detail in the following example:

EXAMPLE II Preparation of cyclic methylene cyanodithioimidocarbonateTwenty-seven and six-tenths (27.6) parts of methylene iodide was addeddropwise to a suspension of 20 parts of dipotassiumcyanodithioimidocarbonate in 80.4 parts of acetonitrile. The suspensionwas stirred 1 hour at room temperature and refluxed 18 hours. The hotacetonitrile solution was decanted; and the residue was treated with20.1 parts of hot acetonitrile, which was combined with the decantate.The acetonitrile was then evaporated and the residue dissolved inacetone. The acetone solution was stirred with charcoal, and ether wasadded to precipitate a high-melting point solid. After filtration, theacetone ether was evaporated from the filtrate and the residuerecrystallized to give the previously unknown cyclic methylenecyanodithioirnidocarbonate.

The cyclic methylene cyanodithioimidocarbonate (M.P. 154-160") preparedby this novel process was found to have the following elementalanalysis:

Calculated for C H N S (percent): C, 27.67; H, 1.55; N, 21.52; S, 49.26.Found (percent): C, 27.68; H, 1.58; N, 21.20; S, 49.04.

(2-(1,3-diethiolaneidene)) urea, a typical type I urea compound, can beprepared by either of the syntheses represented by the followingequations:

S 1101, ether 8 Preparation of (2-(1,3-dithiolaneidene)) urea by theprocesses represented by the foregoing equations is described in detailin Examples III and IV below.

EXAMPLE III Preparation. of (2-(1,3-dithiolanediene)) urea by Process(A) Twenty (20) parts of cyclic ethylene cyanodithioimidocarbonate wasstirred with 219 parts of concentrated hydrochloric acid. After 20minutes the reaction mixture became homogeneous, and the temperaturerose to 38. After standing overnight, the solution was evaporated at 60.The residue was stirred with 88.1 parts of water and EXAMPLE IV Amixture of 20 parts of cyclic ethylene cyanodithioimidocarbonate, 6.7parts of absolute ethanol, and 68.8 parts of anhydrous ether was placedin a flask which had previously been dried and swept with nitrogen. Theflask was cooled to 0, and the temperature was held at 0 while HCl gaswas passed through the mixture. After 3 hours the ice bath was removedand the HCl passed through the mixture for another 4 hours. The reactionmixture was stirred overnight under nitrogen. The fine solid which hadformed was rapidly filtered off, washed with dry ether, and placed in adesiccator over powdered P 0 and NaOH pellets for 50 hours.

A suspension of 20 parts of the above-obtained product and 1.6 parts ofammonia in.20.9 parts of absolute ethanol was stirred first in an icebath and then three days at room temperature. The reaction mixture wasboiled with 139.6 parts of ethanol and was then filtered hot. Thefiltrate was treated similarly with another 139.6 parts of ethanol toobtain additional product. The ethanol was then evaporated, and the twosolids were combined and recrystallized from ethanol.

The product obtained from this novel process was previously unknown(2-(1,3-dithiolaneidene) urea.

Other type II compounds can be prepared by the process illustrated inthe following equations:

5 ll cic niscn -0-on Preparation of 1-phenyl-3-(2-(1,3-dithiolaneidene))urea 29.7 1, 1-diphenyl-3-3(2-(1,3-dlthiolaneidene urea.

Component Dimethylearbamoylchl0ride.

Di phenylcarbamoyl chloride" n-Hexyl chloroiormate 21.1 n-HexylN-(2-(1,3-dithiolaneidene)) carbamate.

Phenyl chloroiormate 20.1 Phenyl N-(2-(1,3-dithiolaneidene)) carbamate.

3-chlorophenyl chloroformate. 24. 5 3-chlorophenyl N-(2-(1,3-dithiolaneidene)) carbamate.

4-ohlorophenyl chloroiormata. 24. 5 4ehlorophenylN-(2-(1,3-dithiolaneidene carbamate.

The compounds identified in Example V and Tables 1 A solution of partsof 2-chloroethyl thiocyanate and 15 and 2 were found to have thefollowing elemental analyses 44.8 parts of thiolbenzoic acid in 115parts of sodium dried and melting points.

TAB LE 3 Elemental analysis, percent Calculated Found M P CompoundEmpirical formula 0 H s o H s degrees-phenyl-B-(2-(1,3-dithiolaneldene)) urea CmHmNzO S2 50. 40 4. 23 26. 9150. 02 4. 06 27. 16 171-178 1,1-dirnethyl-3- (2-(1 ,3-dlthiolaa1eldene))urea CeHl0N2O S2 37. 87 5. 29 33. 70 37. 67 5. 28 33. 55 66-621-(2-chlorophenyl)-3-(2-(l,3-dithlolaneidene)) ure C10HiC1N2OS2 44. 033. 32 23. 50 43. 61 3. 02 24. 09 150-153 1-(3-chlorophenyD-3-(2-(l,3-dithiolaneidene)) urea CmHuOlNaOSz 44. 03 3. 32 23. 50 44. 10 3. 1123. 75 135 136 1- 4-chlorophenyl)-3(2-(1,3-dithiolaneidene)) urea-CmHoClNzO S2 44. 03 3. 32 23. 50 44. 99 3. 50 24. 191- 193 1-(3,4-dlchlorophenyl)-3-(2-(1,3-dlthi0laneidene)) urea. CmHsClzNzO Se 39.09 2. 62 23. 08 38. 60 2. 69 21. 48 191 192-((2-nltrophenyD-3-(2-(1,3-dith1olaneidene)) urea CioHeNaOaSz 42. 39 3.20 22. 63 42. 61 3. 49 23.06 168-171 n,l-diphenyl-3-(2-(1,3-dithiolaneiden6)) urea CIBHHN2O S: 61. 12 4. 49 20. 40 60. 76 4. 1120. 43 191-192 ll-Hexyl N-(2-(1,3-dithiolaneldene)) carbamate-CiQHflNOgSg 48. 55 6. 93 25. 92 47. 98 6. 99 25. 44 Liquid PhenylN-(2-(1,3-dithio1aneidene)) carbamate 1o 0 2 50.19 3.79 26.80 49. 564.46 27. 13 110111 S-chlorophenyl N-(2-(1,3-dithiolaneidene)) carbamatCmHsClNOzSr 43. 87 2.95 23.43 43.46 2. 97 23.87 128-129 4-chlorophenylN-(2-(1,3-dithiolaneldene)) carbamate- CmHsClNOzSz 43. 87 2. 95 23. 4343. 63 3. 09 26. 36 136-138 benzene was refluxed 45 minutes undersulfuric acid dried nitrogen. The reaction mixture was cooled andfiltered to give a crude product. This was dissolved in water andreprecipitated with acetone to give 2-imino-l,3-dithiolanehydrochloride.

A suspension of 20 parts of 2-imino-1,3-dithiolane hydrochloride, 15.3parts of phenyl isocyanate, and 32.3 parts of sodium bicarbonate in121.8 parts of acetone was refluxed 4 hours. As soon as the temperaturereached around 40, gas evolution was observed. The reaction mixture wascooled and filtered. The solid was washed with 384.6 parts of water, andthe water insoluble portion was combined with a precipitate formed whenthe acetone filtrate was poured into 512.8 parts of water to give thecombined crude product. This product was recrystallized to givepreviously unknown 1-phenyl-3-(2-(1,3-dithi0laneidene)) urea.

The foregoing process can be employed to prepare the(2-(l,3-dithiolaneidene)) ureas listed in the following table bysubstituting the indicated parts of isocyanates for the phenylisocyanate employed in Example V.

thiolaneidene)) urea.

This process can also be used to prepare the (2-(1,3- dithiolaneidene))ureas listed in Table 2 below by employing 43.1 rather than 32.2 partsof sodium bicarbonate and by substituting one of the chlorides orchloroformates listed in the table in the parts indicated for the phenylisocyanate employed in Example V.

An alternative preparation of 2-im1no-1,3-dlthiolane hydrachloride fromcyanogen chloride and 1,2-ethanedithiol has been described by R. W.Addor, J. Org. Chem. 29, 738 (1964).

1-phenyl-3-(2-(1,3-dithiolanediene)) thiourea, a type III compound, canalso be prepared by the process of Example V. In preparing thiscompound, however 17.3 parts of phenyl isothiocyanate is substituted forthe phenyl isocyanate employed in the synthesis described in Example V.

The novel 1 phenyl 3-(2 (1,3 dithiolaneidene)) thiourea prepared by thisprocess had a melting point of 117-119 and the following elementalanalysis:

Calculated for C H N s (percent): C, 47.21; H, 3.96; S, 37.81. Found(percent): C, 46.64; H, 4.05; S, 39.08.

(2-(1,3-dithiolaneidene)) thiourea, a type I compound, can be preparedby reacting cyclic ethylene cyanodithioimidocarbonate with thiolaceticacid as shown by the following equation and by Example VI below.

S O S I S \.=N CN .=N t NH,

EXAMPLE v1 Preparation of (2-(1,3-dithiolaneidene)) thiourea Asuspension of 20 parts of cyclic ethylene cyanodithioimidocarbonate and10.5 parts of thiolacetic acid (dried with MgSO in 141.6 parts ofanhydrous ether was cooled in an ice bath to 0 under nitrogen, andhydrogen chloride gas (dried by passing through concentrated H SO wasbubbled through the suspension for 3 hours at 0. The color of thesuspended solid changed from white to bright yellow. The reactionmixture was allowed to stand overnight. The solid was then filtered ofi,washed with 1100 parts of ethyl ether and purified by dissolving in 5%NaOH and reprecipitating with 3 M HCl to give previously unknown(2-(1,3-dithiolaneidene)) thiourea.

The (2-(1,3-dithiolaneidene)) thiourea (M.P. 136- l38) prepared by thisnovel process was found to have the following elemental analysis:

Calculated for C H N S (percent): C, 26.94; H, 3.39; 8, 53.95. Found(percent): C, 26.50; H, 3.54; S, 54.22.

The novel compounds of the present invention are growth'regulators for avariety of biological systems as shown by the following examples.

EXAMPLE VII 8 EXAMPLE 1x A high degree of nematocidal activity is alsodemonstrated by the compounds of the present invention. To show this, asolution of 5 parts of cyclic methylene cyanodithioimidocarbonate with41 parts of polyoxyethylene sorbitanmonolaurate in 5000 parts ofdistilled water was prepared. A solution of 41 parts of polyoxyethylenesorbitan monolaurate in 5000 parts ,of distilled water was prepared foruse. as a check. 1 r Y Mixed populations of nematodes (Rhabditis andPanagrellus spp) were cultured on cellulose sponges and fed with potatobroth. These were extracted by washing from V the sponges, sieved,passed through Baermann apparatus until dry; The-granular compositionwas applied manual- Compound-Cyclic methylene cyanodithioimidocarbonate:Percent of kill A 97 B 98 C 100 D 100 E 100 As shown by Table 4, cyclicmethylene cyanodithioimidocarbonate, a typical compound of the presentinvention, possesses outstanding pre-emergence herbicidal activity.

EXAMPLE VIII The compounds of the present invention also demonstrate ahigh degree of post-emergence herbicidal activity. This is shown by thefollowing test.

Spray compositions were used in the test. These were prepared in thefollowing manner. Six and eight-tenths (6.8) parts ofcyanodithioimidocarbonate for a five pound per acre rate, seven parts ofpolyoxyethylene sorbitan monolaurate, and 10 parts of denatured alcoholwere thoroughly mixed together with a micro mortar and pestle. Themixture was then diluted with 5000 parts of water.

These spray compositions were applied with a sprayer to Poa pratensis(A), Digitaria sanguinalis (B), Poa annua (C), Amaran thus retroflexus(D), Barbarea spp (E), andTrifolium repens (F) when the first trueleaves had appeared (approximately three weeks after sowing). Similarplants were left untreated as a comparative check. Twenty-one days afterapplication percentage of kill was calculated using untreated plants asstandards. The results are tabulated below.

The tabulated data shows that the tested compounds typical compounds ofthe present invention have a high degree of post-emergence herbicidalactivity.

to remove organic matter, and concentrated with Buchner funnels.

Test vials were filled two-thirds full of sand. One milliliter'ofuema'tode solution with approximately 100' nomatodes in it Was addedto each vial. Two hundred fiftyfive (255) parts ofcyanodithioimidocarbonate solution was then added via a microli-tersyringe. Test vials simi larlycont'aining sand and nematocide solutionwere made up, and 255 parts of water-polyoxyethlyene sorbitanmonolaurate solution containing no cyanodithioimidocan bonate was addedas a comparative check. All vials were loosely capped, incubated at 70for 48 hours, then poured into petri dishes andset aside for anadditional 48 hours. Percentage of kill was calculated with aTri-simplex Bausch and Lomb viewer using untreated vials as standards. a

At a rate of 50 ppm. the cyclic methylene cyanodithioimidocarbonatekilled 100% of the nematodes. The foregoing data shows that cyclicmethylene cyanodithiomido' carbonate, a typical compound of the presentinventior possesses a high degree of nem'atocidal activity.

EXAMPLE X Cyclic propylene cyanodithioimidocarbonate was found to giveexcellent selective control of bentgrass (Agrostis spp) in Kentuckybluegrass (Poa pratensis) turf. This selective herbicidal activity wasshown by the following test.

Five (5) parts of cyclic propylene cyanodithioirnidocarbonate and 5000parts of water were thoroughly on the Kentucky bluegrass turf.

EXAMPLE XI The compounds of the present invention also possess a highdegree of fungicidal activity. This is shown by the following test.

For a 0.1 pound of cyanodithioimidocarbonate per acre rate test, ll partof cyanodithiomidocarbonate, 41. parts polyoxyethylene sorhitanmonolaurate, 396 parts acetone, and 500 parts water were mixed togetherin a pestle? A 0.2 milliliter portion of this mixture was mixed with 2.8milliliters of water and 60 milliliters of nutritive agar.

Twenty (20) ml. of the resulting mixture was poured into a petri dishand allowed to set. Three-sixteenth (7 inch plugs of Rhizoctonia solani(A), H elmz'nthosphorium sativum (B) and Fusarium roseum (C) were placedon the agar mixture and incubated at 80'. Similar fungal plugs wereplaced on untreated agar as a comparative check. Seven days laterpercentage of kill was calculated using plugs on untreated agar asstandards. The results are tabulated below.

2 Appropriate variations were made in the proportions only in preparingthe compositions for the 10 pound per acre tests.

TABLE 6 Rate, Percent of kill pounds Compound per acre A B 0 Cyclicethylene cyanodithiomidocarbonate m 100 100 Cyclic propylenecyanodithiomido- 1 98 98 III:

10 100 100 100 (2(l,3-dithiolaneidene) urea 0 1 86 Trace 46 PhenylN-(2-(l,3-dithiolaneidene) carbamate 1o 0 75 Cyclic methylenecyanodithioimido- 0 carbon e 1,1-dimethyl-&(2-(1,3-dithiolaneidene) urea10 89 84 40 The foregoing data shows that the exemplary compounds,typical compounds of the present invention, possess a high degree offungicidal activity, in many cases at the remarkably low applicationrate of only 0.1 pound per acre.

This invention may be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The presentembodiments are, therefore, to be considered in all respects asillustrative, and not restrictive, the scope of the invention beingindicated by the appended claims rather than by the foregoingdescription; and all changes which come within the meaning and range ofequivalency of the claims are, therefore, to be embraced therein.

What is claimed and desired to be secured by Letters Patent is:

1. Cyclic methylene cyanodithioimidocarbonate.

2. The process of preparing cyclic methylene cyanodithioimidocarbonatecomprising the step of r efluxing methylene iodide with dipotassiumcyanodithiomidocarbonate in acetonitrile.

References Cited UNITED STATES PATENTS 4/ 1962 'Brack 167-33 2,547,7244/1951 Sundholm 260-327 3,057,875 10/1962 Brown 2 60-327 JAMES A.PATTEN, Primary Examiner U.S. Cl. X.R.

UNITED STATES PA'KENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,755, 363 Dated August 28, 1973 Inventor s Richard J. Timmons et a1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

The inventor Richard V. Timmons should be changed to -Richard J.Timmons--.

Table 3, 5th entry, "1-4" should be -l-(4--.

Table 3, 7th entry, should be ---l- Table 3, 8th entry, "n,l" should be-l,l--.

Table 3, 9th entry, "ll-Hexyl" should be -nHexyl-.

Table 3, 10in entry, "4.46" should be -'-4.26-'-.

Table 3,

Columns 5 &-6, 1st

entry, "171-178" should be -171-173--.

Columns 5 & 6, 2nd "66-62" should be -66-68-- entry,

Columns 5 a 6, 3rd "150-153" should be ---1so-1s2--.

entry,

Column 6, first line following Table 3, "dithiolanediene" to-dithiolaneidener-.

Signed and sealed this 16th day of April 1971;.

(SEAL) Attost:

EDWARD I1.l- LETCHER,JE'L. C. MARSHALL DANN Atte sting OfficerCommissioner of Patents FORM PO-lOSO (10 69) USCOMM-DC 60376-P69 ".5.GOVERNMENI PRINTING OfflCQI: I969 0-366-334

